Manufacture of artificial materials such as fibers



Patented Dec. 30, 1941 murscruns or ARTIFICIAL mritams SUCH-AS mass 7Paul Schlack, Berlin-Treptow, Germany, assign-' or, by mesneassignments, to Walther H. Duisberg, New York, N. Y.

No Drawing. Application October 21, 1935,'-Se- Y final No. d7,638. InGermany November 1,

3 @laims.

My present invention relates to the manufacture of artificial fibersfilms having an increased afllnity for acid dyes. More particularly, itrelates to the production of such fibers and films from cellulose estersand others and thelike organophil polymers.

Artificial products, such as artificial threads or films of organiccellulose derivatives and other highly polymerized organic substances,for instance, polyvinyl esters, partially saponifled polyvinylesters,polyvinyl acetate, polyacrylic acid tabellen, 7th edition, vol. I, No.169), Alizarine Direct Bue A (Schultz Farbstofitabellen, 7th edition,vol. 2, page 9), Alizarine Direct Violet ER (Schultz Farbstofltabellen,7th edition, VOL-II, p. 10) Alizarine Yellow RW (SchultzFarbstoiftabellen, 7th edition, vol. I, No. 66), and even then thedye-bath is only very poorly exhausted.

It is known that the aflinity of cellulose esters or others to suchdy'estufls can be considerably improved by introducing basic radicalsinto the cellulose molecule. The various methods hitherto proposed forthis purpose are, however, tiresome, costly and in most cases affect thequality of the product considerably.

It has already'been proposed to incorporate proteins with organiccolloids, particularly cellulose acetate. Such heterogeneous mixturescan material, into products having a basic character.

For the'purpose of the invention a large number of artificial resinscomes into consideration which hitherto have found no, or but littleapplication, or have not been known. A series of such substances arelisted below but the list is by no means exhaustive;

1. Condensation products amines and formaldehyde, for instance, thepolymeric 'methylene-amino-benzylaniline obtainable as described inGerman specification No. 121,506 from ortho-toluidine and formaldehyde.

2. Basic ethers of condensation products from carbonyl compounds, forinstance the reaction products of Novolacs' withp-chlorethyl-diethylamine. Of these products especially those areadvantageous which, in addition to the etherified phenol hydroxylgroups, contain radicals which improve solubility, for example, carboxylgroups esterified with aliphatic monoor poly-hydric alcohols, acylamido-groups, sulfamido-groups or alkoxy-groups.

The products are obtainable by boiling a solution of a Novolac in analcoholic solution of potassium hydroxide or in a solution of sodiumalcoholate with p-chlorethyldiethylamine until solutions.

be made into artificial products only with difflculty and yield productswith unsatisfactory or at best moderate physical properties, at allevents when the protein content is sumciently greatto ensuresatisfactory dyeing.

It is therefore an object of the present invention to provide a processfor increasing considerably the affinity of suchmaterials for dyestuffsor,dyestutf derivatives or dyestuil components having acid groups,without substantially damaging the physical properties of saidmaterials. For this purpose there is added to the solution from whichthe material is to be formed one or more synthetic bodies of highmolecular weight which are soluble in organic solvents and insoluble orsparingly soluble in water and which contain basic radicals in freecondition or bound in salt-like manner, or can be converted byhydrolysis, reduction or treatment with an allqlating agent, either inthemselves or in the formed the phenol-hydroxyl groups are completelysubstituted. The products are insoluble in alkaline tained in the airmust be excluded in the reaction in order to obtain light products. Avery valuable product is for instance obtained by boiling thecondensation product obtained from salicylic acid dimethyl-amide andformaldehyde in the presence of hydrochloric acid, with'fl-chloroethyldlethylamine in the presence of sodium alcoholate andabsolute alcohol.

3. Products of reaction of chlorinated methylene-alkyl-aryl resinsobtainable from xylene and acetate, chloracetates of hydroxyalkylatedNofrom aromatic The influence of the oxygen con--.

volac' and the like. Products oi reaction oi polyvinyl chloracetatewith'amines are described in Ge an specification No. 542,778. It is oiadvantage to carry out the reaction in a solvent or an amine is carriedout under pressure at a anew-,sss

in to which toluenesuiio-cellulose is made irom alkali cellulose. Theinteraction with ammonia temperature oi 60 to 100% C. An excess oi amineiree irom hydroxyl groups. lolyglycid is de-; '1 prefer'gbly y scribedin German Patent No. 575,750. The chloracetate is obtainable by treatingpolyglycid with chloracetic anhydride, whereby chloracetic acid ispreferably used as a solvent.

5. Products oi reaction oi ammonia or amines with ethers of compounds oihigh molecular welght'having active halogen, particularly compoundshaving 1,2-halogeno-hydroxy-groups, ior instance, the products oireaction oi epichlorhydrin on ethoxylated Novolacs," partiallysaponiiied polyvinyl esters or the like, as well as the glycidesobtainable by chiorhydrins with alkali. For the production oi thechlorohydroxypropylethers epichlorhydrin is caused to react on Novolacs"or partially saponiiled polyvinylacetates under pressure and in thepresence oi boric acid, dimethylsuliate, toluenesulionic acid or asimilar acid catalyst. A reaction temperature between 130 and 1'70 0. is

maintained.

6. Polymerization roducts of unsaturated compounds which contain basicnitrogen or are capable oi conversion by saponification or reductioninto products having basic nitrogen such as polymerization products oivinyl ethers or divinyl ethers of amino-hydroxy compounds, for instance,the polymerization product irom 8- hydroxy-quinoline-vinyl-ether andproducts oi reduction thereoi, p lymerizates of para-acettreatment oithese amino-styrene or para-nitro-styrene. Polymer- 85 ization productsoi this kind may be obtained,

ior instance, accordin to Brit. Patent 407,997.

'7. Basic amides of polymeric carboxylic acids,

ior instance, the product of condensation oi'polyacrylic acid amide orpartial amidated poly- 4 acrylic acid methyl ester and di-methylamino'methanol or analogues thereof.

For this condensation a polyamide is reacted with di-methylaminomethanolobtainable in known manner irom 1 molecular proportion oi formaldehydeand 1 molecular proportion oi diethylamine in an autoclave in a suitablesolvent containing preferably hydroxyl groups, ior instance,methylglycol. Preferably there is added the halogen representing theanion by an organic anion, for instance by the radical oi acetic acid. I4

9. Soluble products oi the reaction oi ammonia or amines withsulfo-esters oi 'polyhydroxyl compounds, :0! example.

toluene-suliopolyglycide.

Toluenesuliopoly lycid with toluenesuliochloride on the sodium salt ofpolyglycid in a manner analogous to that accorda weakly basic catalyst,ior instance, a tertiary The up the products in the presonce oi a largeamount oi alcohol, and. to replace is obtainable by reaction 5saponification amounting to about 3-6 per Particularly valuable are thebasic derivatives oi the polymerisates or mixed polymerisates oiunsaturated compounds and basic derivatives 0! polyglycides. In the caseof these bodies suitable choice oi the degree oi polymerisation leadsparticularly easily to the desired degree of solubility;

moreover, the stability. to light is in general quite basic nitrogenunited with aliphatic or hydrc-,

cyclic nuclei. The basic nitrogen maybe wholly or in part in the form ofquaternary ammonium groups, so far as the solubility in the inorganicsolvents is ensured by the nature oi the anions or by other groups inthe molecule.

The described basic compounds are generally sparingly soluble or presentin iorm oi the free base. In iorm oi their salts, ior instance, in iormoi the acetate or the iormate they may be more or less soluble. However,also in this case, they cannot be removed irom the artificial materialsby washing or only slowly. A loss by washing can also be prevented asfar as it is necessary by selecting a suitable anion. Compounds havingthe same anion may be added to the treating baths.

For economical reasons those products are the more important whichcontain nitrogenous radicals which are basic or convertible into basiccondition. In principle, however, such polymerization or condensationproducts are also useful of condensation products of this kind can bestill iurther improved by subjecting to a partial 'saponification thefinished artificial material beiore, 0r simultaneously with a treatmentior the purpose oi strengthening the basic properties. If desired thesaponification can be conducted during the casting or spinning operationor directly following the same by means oi any known saponiiying agent,ior instance, an alkali in water or a solvent containing hydroxyl, anaqueous solution of a salt oi alkaline reaction such as sodiumcarbonate, sodium silicate, sodium phenolate, sodium sulfide, trisodiumphosphate, ammonia or an amine. The saponiiying solution may contain anaccelerator oi saponiilcation, ior instance, an alkali salt or aquaternary ammonium salt, in particular one having a capillary activeradical, for instance, a carbon chain with more than 8 carbon atoms inits cation, also a butler substance, a protective colloid, a wettingagent or a swelling agent. It is not always necessary to produce adeepsaponiflcation. A feeble cent which, ior example, when using ammoniaor an insoluble in water when,

amine may proceeduniformly throughout the interior of the fibers,considerably increases the aillnity. In this case the amnity forinsoluble dyestufis, for basic dyestufis and for diazotisable amines ismore or less completely retained. In the case of a feeble saponificationthe afiinity for these dyestuffs and dyestuif components may indeed beincreased. Many acid dyestuffs, which, like cyanine B, dye acetate silkonly fe'ebly even in the presence of the basic resinous additions, yieldbrilliant dyeings of normal strength and good properties of fastnessafter saponification.

erations, can be locally efiected either by prlnt-' ing, spraying orstencilling with a thickening agent carrying the necessary agent for thetreatment or by impregnating the goods locally with a reserve, forexample, a wax reserve or with a paste which contains an agentpreventing alkali attack on the fiber, for example, an alkali salt of aphenol sulfonic acid.

When a reducible nitro-group or nitroso-group is present in the addedresinous substance the saponification may be produced with advantage bymeans of sodium sulfide. There may be added to the saponifying, agent anadditional reducing agent such as hydrosulfite or a stannlte. If thereduction is performed independently of the saponification in an acidmedium stannous chloride or a titanous salt or other known acid reducingagent may be used.

The following examples illustrate the invention:

Example 1.Acetyl cellulose having a content of 53 per cent of aceticacid and the artificial resin obtainable from ortho-toluidine andformaldehyde, as described in German Patent No. 121,506, are dissolvedtogether in glacial acetic acid or ethylene chlorhydrinand the solutionis cast to produce a film. The latter is dyed by Orange II substantiallymore intensely than a similarly made film of pure acetyl cellulose.

Example 2.-A solution of 400 parts of acetone, 92.5 parts of acetylcellulose having 54.5 per cent of acetic acid and 7.5 parts of a basicartificial resin made by treating an acid condensation product fromphenol mol.) and formaldehyde (7 mp1.) with diethylamine andformaldehyde is spun by the dry-spinning process; the artificial silkthus obtained is dyed substantially more deeply by Alizarine Direct BlueA than a similar material made from pure acetyl cellulose. The dyeingson pure acetate artificial silk are also less fast to water. A similarresult is produced with a solution of isfiltered from the crystallizedsalt and mixed acetyl cellulose having an acetic acid content of 53.5per cent in acetone in the proportion such that 7.5 per cent of basicresin is precipitated on the acetyl cellulose. The artificial silkobtained eration is dyed by means of acid dyestuffs, for instance,intensely with Orange II and Alizarine Direct Violet ER. The brownishcolour of the silk can be removed by a weak bleach.

Example 4.To a solution of acetyl cellulose having an acetic acidcontent of 53.5 per cent of acetic acid in acetone there .is added asolution of the basic resin from poly-glycide-chloracetate andmorpholine in a proportion'of 10 per cent of the acetyl cellulose. Thesilk obtained by dryspinning has a high afinity for acid dyestuffs.

Example 5.To a solution of ethyl cellulose having 45 per cent of ethoxylthere are added 10 per cent (calculated on the ethyl cellulose) of thebasic resin obtainable-by the action of morpholine on the chlorinatedcondensation product from xylene and formaldehyde. The films obtainedfrom this solution can be dyed with acid dyestufi's.

Example 6.A solution is prepared from 90 parts by weight of acetylcellulose having an acetic acid content of 53 per cent, 10 parts of theartificial resin obtainable as described in German Patent No. 121,506from ortho-toluidine and formaldehyde and 560 parts of glacial aceticacid; the solution is cast into the form of a film. The film ispartially saponified by 12 hours i'mmersion in an ammonia solution of 10per cent strength, it is intensely dyed by acid dyestufi's such asOrange II.

Example 7.An artificial silk made by the dryspinning process from anacetone solution and consisting of lose having an acetic acid content of54.5 per cent and 7.5 parts of an "artificial resin made from phenolformaldehyde and dimethylamine, is saponified in the form of a fabricwith a caustic soda lye of about 0.2 per cent strength containing 10grams of sodium acetate per liter, the temperature being 50 C. and theoperation being continued until there is a diminution of dry weightamounting to 8 per cent. This fabric can be dyed with acid dyestufis,for instance, cyanine B. The fastness of the dyeings can be improved byan after-treatment with an aqueous solution, feebly acid with aceticacid, tificial resincontained in the silk.

Example 8.--To a solution of ethyl cellulose in a mixture of benzene andalcohol there is I added a proportion of 10 per cent of the celluwhenusing an artificial silk which consists of Example 3.A solution ofpolyvinyl chloracetate in acetone is allowed to stand in admixture with2 mol. piperidine at 40 C. until no more piperidine hydrochlorideseparates. The solution lose ether of the resin obtainable by reactionof the chlorinated condensation product from xylene and formaldehydewith sodium mercaptide and the artificial product obtained from thesolution is subsequently treated with methyl iodide at 70 C. Theproducts have an increased afiinity for acid dyes such as Orange II,Metanil Yellow, Fast Red AV and the lik Example 9.A- solution ofcellulose acetate containing 53 per cent of bound acetic acid, in amixture of acetone and alcohol (70:30) to which have been added 7.5 percent (calculated on the cellulose acetate) of the condensation producttreated with nitrous acid and obtained by condensation offi-chlorethylmethylamine with the Novolac resin obtained by condensationof 10 molecular proportions of phenol and 7 molecular proportions offormaldehyde in the presence of a mineral acid, is spun into an aqueousby the dry-spinning op 92.5 parts by weight of acetyl celluof the ary of.dioxane, 50 grams of sodium salicylate and 20 grams of acidzinc-formaldehyde-sulfoxylate per liter. The threads are cut intostaples and are treated with a percent solution of stannous' chloridecontaining per cent of salicylicacid (calculated on the fibers) .at 40to 60C. in order to completely split oi! the nitroso groups. Thefinished product is intensely dyed by acid wool dyes, for instance, suchfrom the aminoanthraquinonesulfonic acid.

Example 10.A spinning solution which contains besides cellulose acetate10 per cent of a resin obtained by heatingp-[methylthiomethyll-benzenesulfamide (made ofp-chlormethylbenzene-sulfamide and sodium methylmercaptide) andformaldehyde in the presence of formic acid, is spun into a neutralprecipitating bath in which the toluene sulfonic acid methylester hasbeen emulsified. The product is subsequently to its its productionheated at 40 to 70 C. in the presence of prepared chalk. After thistreatment the product has an increased afllnity for acid dyes, forinstance, Orange II. It may be assumed that part of the thioether groupshave been transformed into methyl sulfonium groups.

Example 11.A product obtained by condensation of/ p-butyl-phenol withformaldehyde in I the presence of hydrochloric acid is reacted with thecalculated quantity of p-bromethylamine in alcoholic alkaline solutionand the product of reaction is mixed with the calculated quantity ofchloral. This artificial resin is added in a quantity of 6 per cent(calculated on the cellulose derivative) to a solution of a moderatelyethylated cellulose acetate in a mixture of benzene-and alcohol. Byafter-treating films .made

amaze-1a from this solution with dilute formic acid containing 6 percent of salicylic acid calculated on the film mass, a strong afnnity foracid dyes is produced.

What I claim is: Y

1. A process of producing artificial fibers and foils with an increasedcapacity of being dyed by acid dyestuffs which comprises dissolvingcellulose acetate and an orthotoluidineformaldehyde resin in glacialacetic acid and making said solution into films or artificial fibers.

2. A process of producing artificial fibers and foils with an increasedcapacity of being dyed by acid dyestuffs which comprises allowing asolution of polymerized vinylchloracetate in piperidine to stand at C.until no more piperidinehydrochloride separates, filtering the solutionfrom said crystallized piperidine-hydrochloride salt, mixing thesolution with a solution of acetyl cellulose so that 7.5 per cent ofresin is combined with the acetyl cellulose, and making the solutioninto an artificial product.

3. A process of producing artificial fibers and foils with an increasedcapacity of being dyed by acid dyestufis which comprises adding to thesolution of a moderately ethylated cellulose ethylether in a mixture ofbenzene and alcohol 6 per cent calculated on the cellulose ethylether ofan artificial resin obtained by treating a pbutyl-phenol formaldehyderesin with p-bromethylamine in alcoholic alkaline solution and theartificial resin thus obtained with an equivalent quantity of chloral,making the solution into an artificial product and treating saidartificial product with dilute formic acid containing 5 per cent ofsalicylic acid calculated on the treated artificial product.

. PAUL SCHLACK.

